CA2208100A1 - Azametallocene polymerization catalysts - Google Patents

Azametallocene polymerization catalysts

Info

Publication number
CA2208100A1
CA2208100A1 CA002208100A CA2208100A CA2208100A1 CA 2208100 A1 CA2208100 A1 CA 2208100A1 CA 002208100 A CA002208100 A CA 002208100A CA 2208100 A CA2208100 A CA 2208100A CA 2208100 A1 CA2208100 A1 CA 2208100A1
Authority
CA
Canada
Prior art keywords
catalyst
added
catalyst according
polymer
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
CA002208100A
Other languages
French (fr)
Inventor
Bradley P. Etherton
Sandor Nagy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Equistar Chemicals LP
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2208100A1 publication Critical patent/CA2208100A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

Disclosed is an azametallocene polymerization catalyst having general formula (I), where L is a lignad, or mixture of ligands, each having 4 to 30 carbon atoms and containing at least two fused rings, one of which is pyrrolyl ring, Cp is a ligand containing a cyclopentadienyl group, B is a Lewis acid, Y is a halogen, alkoxy from C1 to C20, siloxy from C1 to C20, or mixtures thereof, M is titanium, zirconium, or mixtures thereof, m is 1 to 4, and n is 0 to 2, p is 0 to 2, q is 0 to 1, and m + n + q = 4. The catalyst is useful in polymerizing unsaturated olefinic monomers such as ethylene.

Description

= AZAMETALLOCENE POLYMERIZATION CATALYSTS
Backctround of the Invention This invention relates to azametallocene catalysts useful for polymerizing olefins such as ethylene and other unsaturated monomers. In particular, it relates to catalysts having at least one ligand that contains a pyrrolyl ring bonded to a transition metal.

Until recently, polyolefins have been primarily made with conventional Ziegler catalyst systems. These catalysts typically consist of transition metal-containing compounds and one or more organometallic compound. For example, polyethylene has been made using Ziegler catalysts such as titanium trichloride and diethylaluminum chloride, or a mixture of titanium tetrachloride, vanadium oxytrichloride, and triethylaluminum. These catalysts are inexpensive but they have low activity and therefore must be used at high concentrations. As a result, it is sometimes necessary to remove catalyst residues from the polymer, which adds to production costs. Neutralizing agents and stabilizers must be added to the polymer to overcome the deleterious effects of the catalyst residues.
Failure to remove catalyst residues leads to polymers having a yellow or grey color and poor ultraviolet and long term stability. For example, chloride-containing residues can cause corrosion in polymer processing equipment.

Furthermore, Ziegler catalysts produce polymers having a broad molecular weight distribution, which is undesirable for some applications such as injection molding. They are also poor at incorporating c-olefin comonomers. Poor comonomer incorporation makes it difficult to control the polymer density. Large quantities of excess comonomer may be required to achieve a certain density and many' higher c-olefins, such as 1-octene, may be incorporated at. only very low levels, if at all.

Although substantial improvements in Ziegler catalyst systems have occurred since their discove:ry, these catalysts are now being replaced with the recently discovered metallocene catalyst systems. A metallocene catalyst typically consists of a transition metal compound which has one or more cyclopentadienyl ring ligainds. They have low activities when used with organometallic compounds, such as aluminum alkyls, which are used with traditional Ziegler catalysts, but very high activities when used with aluminoxanes as cocatalysts. The activities are generally so high that catalyst residues need not be removed from the polymer. Furthermore, they produce polymers with high molecular weights and narrow molecular weight distributions. They also incorporate a-olefin comonomers well. However, at higher tiemperatures metallocene catalysts tend to produce lower molecular weight polymers. Thus, they are useful for gas phase and slurry polymerizations of ethylene, which are conducted at = about 80 C to about 95 C, but they do not generally work well in solution polymerizations of ethylene, at about 150 C
to about 250 C. The polymerization of ethylene in solution is desirable because it allows great flexibility for producing polymers over a wide range of molecular weights and densities as well as the use of a large variety of different comonomers. One can produce polymers that are useful in many different applications, for example, high molecular weight, high density polyethylene film useful as a barrier film for food packaging and low density ethylene copolymers with good toughness and high impact strength.

One of the characteristics of metallocene catalysts is the presence of 7-bonds between one or more cyclopentadienyl ring-containing ligands and a transition metal. These bonds are moderately strong and stable. In contrast, r-bonds between transition metals and pyrrolyl ring-containing ligands are relatively unstable. Although these nitrogen-containing ligands form unstable r-bonds, analogous ligands with other Group VA elements (P, As) form stable bonds. King (Inora. Chem., 1964, 3, 796) and Joshi (J. Oraanomet. Chem., 1964, 1, 471) found that the pyrrolyl analog of ferrocene was less stable and had indications that pyrrolyl ligands tended to form a-bonds. Van Bynum et FE2-25-H7 OS:52 FRGbI=Griz PATEhCA 0208100 1997-06-181D712 2B83249 PAGE 7/2^, al. prepared 2,5-di.taethylpyrrole derivatives of Zr and showed that there was no n-bonding to the Zr atoms in these compounds S~li-m., r1.9$ y, 64, 13 04 ). La d a.po et 3l . showed that (SaI3: 9 indole complexes with iridium also formed v-borids to the transition metal (Tngi~ Ch&yn., 1990, 29, 4172). A recent review of the subject of g-bonded pyrrolyl-containing ligands (s. Zakrezewski, $=e~. yaies, 2990, 31, 383) reemphasized the -~nstabi2i.ty of these types of cnmplexas.

Database WPI AN 68-29949q, IT-A-778 386 di.sclosed 9-indolyY and If-ca.rba.zy1 derivativea af titaxxium llk= t.i.tanit=-tet.r az ndoly l or ti taniub.-tetracaryaayl and ~-~eir t_~e as ZiCBlcr-satta C-aa.ta1ysts. L'P-A-0 a3-7 O82 discYr.rses irtcY4lyi. aLnd oar~~oly1 xlrconz.am camgcunds as o? ~fsn ~~13,"^er=~~t=~n &-ata-i.y-ats tcbq4sthax Lri+--h an a3.uaxinoxana -t'seim pa.~Q ~2:, 52-57 and olaim. 14 j. A similar disclosure can be found in EP-A-~ 574 794 3.-17s Pac~~~ 3-$ , aays 4, 1 s.raos ::5.-4l i Ajz=arv of the Tnventi on We have disccrvered certain novel azamatallrscene compounds u ich are usat,u-' . as. &--7.ymer=Lation catalvsts ^:Te.r zx wide of polymer lzat~on condition3.. ?hese compounds a:L= l.zavc -aT
ieam-L- oas 21qand eoa~aesasirsg a pyr:-alyl group, vhselz ira Aa n? r ~ouan-cont.a.~*~ing 5-membsre% resonance ring. V,e ayrrolyl +trbuYr ear, form a bond to a tr2tnaYt.i.cn mw.taY atom. These compound5 are uuod in conjunction with a Gc<,-ataJ.yst which is t;ra3ca-1# v- an alumi.noxine. it is surnris :Lna that conpou-nds containing a pyrrolyl group are- u$eftal as p8lymerizatifs"ir, 4 *pMENDE4 SHEET

i F-EB-25-97 G39 = 5'8 FROM : OYY PATENCA 02208100 1997-06- 18 D: 7 1 8286 catalysts because it is well known in the catalyst art that rLitrogen-cantai.rs4.n4 compounds are frequently catalyst poisons.
However, we ha.tre found that not only are these compounds useful as olefi.zY polymerization catalysts, but that they have good activity at high temperatures and produce high molecular weight polymers with narrow molecular weight clistri3autions_ Tfihe catalysts of this invention perfo= as well as conventional meicallocene.s in incorporating comortoAters such as butene, octene, hexene, and 4-methylpentene-1. They produce color3.ess polymers having s~sperirsr uv s4a~il4 VX a,:;d ~cr.g t~s -sT~=lity. In ac~c~ition, -~iae cama%y~s of ti~..~a irrvftrx~~.~sn a~G
considerably simpler to prepare anci are less expensive taan the anal ogous T-otal Z4cenes _ -4a-ANtiEi~DED S+yEET

. at high temperatures and produce high molecular weight polymers with narrow molecular weight distributions.

The catalysts of this invention perform as well as conventional metallocenes in incorporating comonomers such as butene, octene, hexene, and 4-methylpentene-1. They produce colorless polymers having superior UV stability and long term stability. In addition, the catalysts of this invention are considerably sim ler to p prepare and are less expensive than the analogous metallocenes.

Description of the Preferred Embodiments The catalysts of this invention are transition metal compounds having the general formula [CP]q [L]~ - M - [Y]n []p where L is a ligand, or mixture of ligands, each having 4 to 30 carbon atoms and containing at least two fused rings, one of which is a pyrrolyl ring, Cp is a ligand containing a cyclopentadienyl ring, where two L ligands or an L and a' Cp ligand can be bridged, B is a Lewis base, Y is halogen, alkoxy from C, to C201 siloxy from C, to C20, N(R,) 2, or mixtures thereof, M is titanium, zirconium, or mixtures -97 095e FROM=OXY PATENT CA 02208100 1997-06-187162883249 PAGE

i . ~

I thereof, m is a riuiuber from I/to 4,A n is a number from t3 to 2, p is a number from 0 to 2, q is a number fro= 0 to 1, and m+ n + q= 4. In the formttl,a, Y is preferably halogen and is z nOre preferably either chlorine or bromine, but ~ alkoxy groups, such as methoxy (CH~O-) , ethoxy (CH~C"2O-), Qr silt+scy (P,)3SiG-, where R., is alkyl from Ci to cw, should also be mentioned. Also, m, is~ preferably 4 as those catalysts pzoduae polymers having the highest molecular welght at the highest temperature.

_E3 EXampl" of t groups that r-an bi-a usa3 :":aoiude alkyi stxbsti.tuted pyrrolyl. rings, N
CR~~

sts~~ as 2-~Q~ylpyrrtsz~.1, ~~~a?-3.~rvS.ZrZ, ~, d im.ethylpyrrolyl , 2, 5-r3i=tsar t=butylpyrroly3. , aryl sttEistitu.te?- py~-^ly3 r:.r.q= s.uCh as c-pR=_nylpyrrolyl, 2,5-"i 5 dYphrlnVl.pyra--aly1, issdalyl, aiky3 sul;Patituted in3oZyZs [wg}
ANicNNDFD SHEET

-97 9 = 59 FROM = 05{Y PATENT Urrr~x iL~nav .

' i .

~ such as 2-znethylindolyl, 2-tert-]zutylindolyl, 3-butylindoly2, 7 methyl:'sndo3.yl, 4,7-dimethylindolyl, aryl substitutad indolyls such as 2-phany3, indolyl , 3-phenylz.xadolyZ, 2-naphthyli.n.dolyl, isoi.ndolyl, and alkyl and ~ aryl substitut+ed isoindolyls (a) ,.s and r-arbaZclyl and a.Iky3, substs .-uted N

Tn th& faXmulas, each R is pr-=:Ear'ksly issdcpcszdcntly saI6cted from hydrogen, as.)W1 'AEro~ - t~o C=a, amd aryl from fft6 4- o ^ IQ and ~,s i,s I to 4. fiho al]ty1 and ,a=-y1- ssub=;it:uornt=

l~ on tha pyrrolyl rirng-,;:vnta.ininq ? iga..d a..ra not an the I7t]. t7C`t1Qe25 t'tt9m 3 ?3 the r 4 n!y* jut ara ::i . ..C erirban aZcm5 of .

AMENDED SHEET

CA 02208100 1997-0(-18:7162H63249 PAGE 11/2' FES-'25-97 05 59 FROM : OXY PASEfIT

the 'riltg. PartiCularly preferred L ligands are the oarbazoZyl and Ct to C4 alkyl i.ndolyls in the 2 or 7 positio,n, or in both positions, because an aYkyl in the 2 positYon prevents the formation of di3aers, ~r--Carbazolyl- and indolyi-based catalysts produce high activity and superior performa.nce at high polymerization tetaperature.s, giving high molecular weights which means a tougher polymer and better isapact strength and better tar.sile pragerties. The formuIas Aqj exclude the use of only man1b~' " pyrrQlyl 7t1Lt7`' arr .47w2c /O Q/f ~YG1,s. ~r G fv n~
groups ~.`'~.
~~
~Zqancl- h~--ausa thormo catalysts do not seem to work well (see CaaT-ara tive 2xampl cs ) .

EXantplee of Lewis bases, B, which Gan be used in this invention f.rtGlude diethyl a'ther, dibutyl ether, tetrahydrofz:rran, and. 1 , 2-dimethoxY,~a-thane _ The Lcwis base B is ':.`c szdua3. ~olvcrr~ and tLe bond betwe= 13 and M is not a covalent bond.

zo The Cp I. igand can be a cyclopentadienyl ring with o, ta 5 sub=titue.nt y2--o,spo., ~R2~r pN9ENDED SREET

where each substituent group, R2, is independently selected from a C, to C20 hydrocarbyl group and r is a number from 0 to 5. In the case in which two R2 groups are adjacent, they can be joined to produce a ring which is fused to the Cp ring. Examples of alkyl substituted Cp rings include butyl cyclopentadienyl, methyl cyclopentadienyl, and pentamethylcyclopentadienyl. Examples of fused Cp ring ligands include indenyl, tetrahydroindenyl, fluorenyl, and 2-methylindenyl. While the Cp ligand can be used in combination with other ligands, it is preferably not present as it seems to lower the molecular weight of polyethylene made at higher temperatures.

Groups that can be used to bridge two ligands include methylene, ethylene, 1,2-phenylene, dimethyl silyl, diphenyl silyl, diethyl silyl, and methyl phenyl silyl.

Normally, only a single bridge is used in a catalyst. It is believed that bridging the ligand changes the geometry around the catalytically active transition metal and improves catalyst activity and other properties, such as comonomer incorporation and thermal stability.

The catalysts of this invention can be prepared in a variety of ways, but they are most easily prepared by starting with a ligand compound. Most of the compounds used as ligands are commercially available, including ,-97 10:00 FROM:OXY PATENT CA 02208100 1997-06-18 DEPARTMENT ID:7162BE3249 PAGE 12/27 ~, .
je indole, pyrrole, and carbazole, as well as some alkyl i,ndole.s. Substituted ligas3da can be made by a variety of methods. Some examples smclude Fri.edel-Crafts aZkylation, a13t.ylatiorx with lithium alkyls, direct synthesis via the Fischer indole synthesis, and the methods described by Bray et aI-- in Z.~ Q=, Sb=.r 1920r5= r6317. A number of other methods are known to those skilled in the art.

In the first step in producing the catalyst, the l i.garid compound is raac--ad with a proton accept4r..
Stoichiometric quc.ntities can be ucad. Exanplss of proton is acceptors include iaethyl-m$gne3ium bromid$r scd.-'.um Lydriae, s$rsdl= metal, and atethy].magne~ium. cLz~.oric~a. The.

proton aocaptor is mathy3. =a.Jr-^..eslvm brcmids becav.se O= aas4-5~
o~ t=.3e. ~ho rGa4"t~on is pr~t~.r~biy gari8~c~ ~~T c~licol'Tiiiy t''~Q i.Qa::"tant3 3..41 an organic sS.llYc.I-, vh-ie~ db" not h'ia'v'e an act..a.va proton such as tet?-a.hys9.rofuacan= mn.3.s,ts e, ar Gtb.y' $t.hQr. An st2aer, sv.ch as ctieth,y? ethcr, is solution should be as concevtrated as possi:vle to reduoG
th.e amourit ot *olvant that muot b4b~ hasdlazdi_ "?4-1-2 reacrti oZ
caaz oc^ur at about -78 t.o about SO C but is priaferab~z z:a in ordar tcs avoid heatind.
Tlae rt.aot3on is ovgr when gas evoY.uticn ceases. r c~L
examplei =axs3alc r~c~s with jewl--hyl ~~a==M bro--IAG te%

ga3 zo'! *ata.<an of an iru3$1Y1 1z.gdnd 3.~'~i tho scalv~stft:

_ _10 A A ACAInFn 0,1-IFr-T

07N + CH3M9Br MgBr + CH4 Ne H
in the next step of the process for making the catalysts of this invention, a transition metal halide, alkoxide, or siloxide is added to the, solution of the ligand compound at a temperature between about -100 and about 0 C. Higher temperatures should be avoided. as *they may cause decomposition of the metal ligand product.
Stoichiometric quantities of the reactants can be used.
The reaction between the ligand compound and the transition metal compound results in the production of the metal ligand catalyst and precipitation of a proton acceptor byproduct, such as magnesium halide. For example, if zirconium tetrachloride is reacted with the indolyl ligand prepared as described in the previous paragraph, the metal ligand catalyst is produced and magnesium halides precipitate:

M Brm + ZrCi Zr ~ J.
~ 9 4 . e i I + 2~Br~ + 2M9CI2 No SUBSTET~iT~ SHc~T ;r~U~E 26i 97 1 0= 00 FROM = OXY PATENT DEYHtt rrttrl r i D= 71S2883249 PACE 1 3/27 ~
~ .
x ~
~ 5 The byproducts are reb2cved by filtration, the solvent is evaporated, and the metal ligand catalyst is colleeted.
wo- we.
whi2e,2' do not wish to be bound by any theory, r believe that the catalysts of this lnvention are single site catalysts because they produce polymers with a ratio of veight average molecular weight to number avezage molecular weight very close to 2. The polymers have a narrow molecular weight di.stri.butzon.

,I 4-2rn3:ir~~;T~=~ a~~ca~~i3ee~s.a po1y,:..sa.sa~~QSs cat-al ys4- of th: -- i:.:: entlon can be prepa-T. ed in a three step ? 5 proc¾du.ro, by first stoicaiom.etrically reactir_g i-n a ~c>l4?ent aGrouD I or II metal ciialk-r 1a-id= w i'th. 4k -tit~$n.l.,a:a or ziroonium cazmpound:

(4-41~'H(~:)2 + M(R3)4-q(CP)q --->
Mi'-q`Rl"RW4-q4CYlq T l4-93WR

t,ih4mra M' ic an alka7.3. 4:,,= alhalirzG carth mctal, preFera.bly lithium, sodium, or magne$ium as those metal dia].kylam.ides are readily available, a.nd R3 is halide, preferably ^hi^~ZAor alkox%de froAt. C; to Cg. Tha R: (al-ky'l rom cz to C,o: group ic preferab3.y C., to Cr, as th,ose compounds are more avai.I.abie. The reaction tempe-ratu.::e --;= not cr.itlual and a tempeerature lbet-:Je-an -i~.~i and =sit'i., audix as rcSZika cu.-`.tz'hZ.o_ Tbi& r4e-ncti--S-oss ;Ia cv~tg3~t~ wnei3 the a3.ka.wi metal or al.3aline eatth metal byproduct, such as l4th4':,3=- :*3:3.oride, Rr+b&ipiicaz&s.

-AMEIRDED S1-IEE~

-g 7 i 0= 0 1 FROM = O}{Y PATENT DEP ytr 1Mniv i Since many tetrakis(dial.kylamido) titanium and zirconium compounds are commercially available, this first reaction is not always necessary.

In the second step of the alternative preparation procedure, the tetrakzs(dYalkylamido) ti.tan.ium or zirconium comp:r is reacted with a compound that contains a pyrrole ring:

X(N(Ri)z)a-qlCP7q 'i" '+++:sr "'- -> (L)nM(N(Rz)z)4-.`4(C:p)q -t- MNH(Rz)2 This reaction will occur over a.w5.de range of temperatures in ttarious solvents including xylen.e, diefi,.hyi ethar, tatr;ilhydrof~xran, and dimatuoxyeuY.ane, but hydrocarbon i5 aalvents~, such as toluene3 are preferred. Preferably, the reaction s.a erbout -7Sac to about 5<7 C.
Ccmp3.etion of the reaction is int':i cated by gas aVoluts.on or the detsctiori of free base using nuclQar maghetic resonance (NMR)=

?'n t.he third r-tep af thc a'1t=~aLi~:~ prapara,tiori pic:..'edurQ, the product of the sa.=.ond r-4--4p x$ reZtct4GY wi-t~
2 zvaip~ ~at r,piaces some or all of the remaining amido crotxps with halogen, a17ccxy, or siloxy groups:

(L) .M(N (Rl) z ) a-M-q (Cpp )Q + nYZ --->
[+cPIg tLlm - M - CY3n + nZN (Fti)z [$]p !
yi7 iera Z is the catiCn1.c portlah o:r +--hs Ym oompot2nti.
I3 ~

AMEI~DED S~EET

Treatment with a halogenating agent replaces the amido groups with halogen. Halogenating agents include such compounds as silicon tetrachloride, hydrogen chloride, methyltrichlorosilane, boron trichloride, hexachloroethane, phosphorus pentachloride, antimony pentachloride, chlorine, and the like. For example, treatment of bis(carbazolyl)-bis(diethylamido)zirconium with two moles of silicon tetrachloride produced bis (carbazolyl) zirconium dichloride.

Since the catalyst is normally used in conjunction with a co-catalyst, it is preferable to dissolve the metal compound in a solvent in which the co-catalyst is also soluble. For example, if methylalumoxane (MAO) is the co-catalyst, then toluene, xylene, benzene, or ethyl benzene could be used as the solvent. Examples of suitable co-catalysts include MAO and mixtures of MAO with other aluminum alkyls such as triethylaluminum, trimethylaluminum, tri- isobutyl aluminum, ethylalumoxane, or diisobutyl alumoxane. The preferred co-catalyst is MAO as it results in high catalyst activity, good comonomer incorporation, and a polymer having a narrower molecular weight distribution. It is preferable not to premix the catalyst and the co-catalyst as this may result in lower catalyst activity.' Rather, the catalyst and co-catalyst are preferably injected separately into a reactor containing the monomer to be polymerized. And, preferably, the co-catalyst is injected first. The amount of cocatalyst used with the transition metal compound can be in a molar ratio ranging from about 1:1 to about 15,000:1.

The catalyst and co-catalyst can also be used on a support such as silica gel, alumina, magnesia, or titania.
Supports are not generally preferred as they leave additional contaminants in the polymer. However, a support may be required depending upon the process being utilized.
For example, a support is generally needed in gas phase polymerization processes and slurry polymerization processes in order to control the particle size of the polymer being produced and in order to prevent fouling of the reactor walls. In order to use a support, the catalyst is dissolved in a solvent and is deposited onto the support material by evaporating the solvent. The cocatalyst can also be deposited on the support or it can be introduced into the reactor separately from the supported catalyst.

Once the catalyst has been prepared it should be used as promptly as possible as it may lose some activity during storage. Storage of the catalyst should be at a low temperature, such as -100 C to 20 C. The catalyst is used in a conventional manner in the polymerization of unsaturated olefinic monomers. While unsaturated monomers such as styrene can be polymerized using the catalysts of this invention, it is particularly useful for polymerizing a-olefins such as propylene, 1-butene, 1-hexene, 1-octene, and especially ethylene.

The catalyst is also useful for copolymerizing mixtures of ethylene with unsaturated monomers such as 1-butene, 1-hexene, 1-octene, and the like; mixtures of ethylene and di-olefins such as 1,3-butadiene, 1,4-hexadiene, 1,5-hexadiene, and the like; and mixtures of ethylene and unsaturated comonomers such as norbornadiene, ethylidene norbornene, vinyl norbornene, and the like.

The catalysts of this invention can be utilized in a variety of different polymerization processes. They can be ut-ilized in a liquid phase polymerization process (slurry, solution, suspension, bulk phase, or a combination of these), in a high pressure fluid phase, or in a gas phase polymerization process. The processes can be used in series or as individual single processes. The pressure in the polymerization reaction zones can range from about 15 psia to about 50,000 psia and the temperature can range from about -100 C .to about 300 C.

The following examples further illustrate this invention.

Example 1 Catalyst Preparation All steps were conducted under a nitrogen atmosphere using conventional Schlenk-line techniques. All glassware was clean and free of moisture and oxygen. All solvents were freed of water, air, and other impurities. This was done by passage over activated basic alumina, collection under nitrogen, sparging with nitrogen, and storage over activated 4A molecular sieves.

Indole (from Aldrich Chemical Company) was recrystallized from hexane. Recrystallized indole (2.34 g) was placed in a 250 ml Schlenk flask which contained a stirring bar and the flask was sealed with a septum.
Diethyl ether (50 ml) was added by double-ended needle to dissolve the indole. The indole solution was cooled to 0 C
in an ice bath. Methylmagnesium bromide (6.70 ml, 3.0 molar) in ether (from Aldrich Chemical Company) was added slowly by syringe while stirring. Gas evolved during this addition. The reaction mixture was stirred for 1 hour.

The ice bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional 1 hour at room temperature.

Zirconium tetrachloride (2.33 g) from Aldrich Chemical Company and used without further purification, was placed in a clean, dry, oxygen-free 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum. Diethyl ether (100 ml) was added by double ended needle. This suspension was cooled to 0 C in an ice bath.
The indole/methylmagnesium bromide product was added to the ZrCl4 suspension over 10 minutes using a double ended FEB-25-97 10:01 FROM:OXY PATEACA 02208100 1997-06-18ID=7162863249 PAGE 15/27 needle. The reaction mixture was stirred for 1 hour. The ice bath was removed and tho- m.i5tture was aZZowed to warm tc room temperature while stirring. The mixture was stirred an additional hoixr at roc-m temperature. The product was an orange slurry. The ether was removed from the slurry by evaporati.on ttnder vacuum. The product was a brown solid.
Toluene (100 m1) was added to this solid and stirred for 2 lxours at room temperature. The solution was recovered by vacuum fxltration using a fine (4 m.icr on) fzittari glass filter. The trslv.ene was xemcsvad by cvaporation under ~~ -v~ec:uu~_ =ii~~ ~a~oQiic~ ~.:~is a soiid wiaiea cortza%n~a d. u w~~
7r~ Blcnsrr.rxtal analysis did not show tcze presfanco Qi cl.

~~i'~7~'tQ~t 7:1t_ Y a:171 pA~77 7"~~
T
TS7,=--^ vonelu=t =d ir ss. ~ d i -1 ~zaini's stec3 a~xzociave at r~a'~~ Dry oxygen-sree. tQluenG
(840 aai) was cirarged to the ~leesn, dry oxygen-free reactor.
Si,x ml of 10t MAO in toluene (frQm pr'thyl Corporation a.ns3 used W3.+4*out f=ther Purifica.tia.n) was addad to tha tr3luana i.n the reactor. No hydrogen or comononter was added to tue reactor. Sufficient ethylene was added to bring the 1. 03!-sE'~
reaotor or=assure f^4.50 psi~. c~s ~s3=utis~n of ozs.taiYst was Prepa=e-mi by dissolvissq 0,.3s04 gra of proc-*u^t in 100 =? o:ff toluEZ:s_ T27--aoa ml of this solution was injectgri into thia reactor ta start a polymerizatioYz.

= ~ 11= AMENDED SNEET

At the end of one hour the ethylene flow was stopped and the reactor was rapidly cooled to room temperature.
The polymer was filtered from the toluene by vacuum filtration. It was dried overnight in a vacuum oven and weighed. The weight of the polymer was 75.2 grams. This corresponded to a catalyst productivity of 69.9 kg/g Zr.
Polymer Properties The melt index of the polymer was measured according to ASTM D-1238, Condition E and Condition F. MI is the melt index measured with a 2.16 kg weight (Condition E).

HLMI is the melt index measured with a 21.6 kg weight (Condition F). MFR is the ratio of HLMI to MI. The polymer density was measured according to ASTM D-1505. The molecular weight distribution of the polymer was measured using a Waters 150C gel permeation chromatograph at 135 C
with 1,2,4-trichlorobenzene as the solvent. Both weight average molecular weight (M,) and ratio of MW to Mõ (number average molecular weight) are used to characterize the molecular weight distribution.

The polymer melting point was measured using a DuPont Instruments 912 differential scanning calorimeter (DSC).
Two heating and cooling cycles were utilized. The melting point was measured on the second heating/cooling cycle.

The heating and cooling rates were 10 C/mir.. Between the two cycles, the sample was held at 200 C for 10 minutes before cooling to 50 C.

The polymer had a MI of 0.086 dg/min and HLMI of 1.82 dg/min. This corresponds to a MFR of 21.2. MW was 162,400 and Mw,/M. was 2.06. This indicates a narrow molecular weight distribution even though the molecular weight was high. The density was 0.9536 g/ml. The DSC melting point was 136.0 C.

Example 2 This example shows that the catalyst can be used with low levels of MAO to produce a high molecular weight polymer. The very high levels of MAO typically used with metallocene catalysts are not needed. The catalyst described in Example 1 was tested under the same polymerization conditions as Example 1 except that 3.0 ml of 10% MAO was used. A one hour polymerization resulted in 26.1 grams of polyethylene. The polymer had a MI of 0.068 dg/min and HLMI of 1.53 dg/min. This corresponds to a MFR
of 22.5.

Example 3 This example shows that the catalyst can be used at high temperatures to produce high molecular weight.

polymers. The catalyst described in Example 1 was tested under the same polymerization conditions as in Example 2 except that the temperature was 110 C. The amount of polyethylene produced was 38.9 grams. The polymer had a MI

of 0.90 dg/min and HLMI of 15.93 dg/min. This corresponds to a MFR of 17.7. MW was 102,800 and MW/Mn was 1.91. The polymer density was 0.9606 g/ml. The DSC melting point was 135 . 8 C.

Example 4 This example shows the effect of higher temperatures and higher levels of MAO on the performance of the catalyst described in Example 1. The catalyst was tested under the same polymerization conditions as in Example 1 except that the temperature was 110 C. The amount of polyethylene produced was 71.3 grams. The polymer had a MI of 1.77 dg/min and HLMI of 32.2 dg/min. This corresponds to a MFR
of 18.2. M. was 79,600 and M,/Mn was 1.68. The polymer density was 0.9601 g/ml. The DSC melting point was 134.9 C.
Example 5 This examples shows the effect of using a different MAO as cocatalyst with the catalyst described in Example 1.
The catalyst was tested under the same polymerization conditions as in Example 3 except that 6.0 ml of polymethylalumoxane (PMAO) S2 (from Akzo Chemical and used without further purification) was used as the cocatalyst.
This sample contained 4.3 mole/liter of aluminum. The amount of polyethylene produced was 81.9 granis. The polymer had a MI of 3.69 dg/min.

Example 6 The catalyst described in Example 1 was tested under the polymerization conditions described in Example 4 except that 20.0 ml of liquid 1-butene was added to the reactor.

The amount of polyethylene produced was 88.9 grams. The polymer had a MI of 11.79 dg/min and HLMI of 233.4 dg/min.
This corresponds to a MFR of 19.8.

Example 7 Catalyst Preparation The catalyst was prepared using the methods described in Example 1. Recrystallized indole (2.34 grams) was placed in a 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum. Diethyl ether (100 ml) was added by double-ended needle to dissolve the indole. The solution was cooled to 0 C in an ice bath.
Methylmagnesium bromide in ether (6.70 ml, 3.0 molar) was dissolved in 50 ml of ether. The methylmagnesiuin bromide solution was added slowly to the indole solution by double-ended needle while stirring. Gas evolved during this addition. The reaction mixture was stirred for 1 hour.
The ice bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional 1 hour at room temperature.

Titanium tetrachloride (1.10 ml) from Aldrich Chemical and used without further purification, was placed in a clean, dry, oxygen-free 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum and 100 ml of ether was added by doiible-ended needle. This was stirred overnight at room temperature to produce a yellow solution. This solution was cooled to 0 C
in an ice bath. The indole/methylmagnesium bromide product was added to the TiC14 solution over 10 minutes using a double-ended needle. The reaction mixture was stirred for 30 minutes, then the ice bath was removed and the mixture was allowed to warm to room temperature. The mixture was stirred two hours at room temperature. The product was a black slurry. The ether was removed from the slurry by evaporation under vacuum to recover a black solid.

Polymeri2ation Testing A solution of.the product was prepared by dissolving 0.500 grams of solid in 100 ml dry, oxygen-free toluene.
After stirring for 1 hour the sample was not completely WO 96/20223 PCTlUS95/116942 dissolved. An analysis of the liquid phase showed a Ti concentration of 5.01 x 10-3 moles/liter. Polymerizations were conducted as described in Example 1, except that 3.4 ml of 10% MAO in toluene was added as a cocatalyst and 30 millimoles of hydrogen were added. No comonomer was added to the reactor. One ml of the catalyst solution was used to start a polymerization and 35.1 grams of polymer was produced after one hour. The polymer had a MI of 0.125 dg/min and a HLMI of 4.75 dg/min. This corresponds to a MFR of 38Ø

Example 8 This example shows the effect of different MAO amounts on the catalyst activity. Solid (0.450 grams) frorn Example 7 was dissolved in 100 ml of toluene. The polymerization conditions were identical to those of Example 7 exc:ept that 3.0 ml of catalyst solution and 10.0 ml of MAO solution were used. In addition, 120 millimoles of hydreigen were added. After one hour 50.1 grams of polymer was produced.
Example 9 This 'example shows the effect of increased hydrogen and 1-butene on the catalyst activity. The polymerization described in Example 8 was repeated except that 12 ml of FEB-25-97 10=02 FROM=OXY PATENT DEPARTMENT ID=7162863249 PACE 16/2' liquid 1-butene and 120 millimcsles of hydrogen were added to the'reactor. In 30 m,inutes 55.5 gra-ms ot polymer was produaed.

Examral.e 10 This example shows the effect of increased hydrogen alone on the , c3talyst activity. The polymerization described in Example 8 was repeated except that 180 mi;.li.mole..z of hydrogcn s ras cttiidv,4 to can+;rcsi. trigF m:31Qa,::..'La~
~.:=eight_ Tn 323 mY ute5 54.9 S3z c%= of }aolyaee--r i,*as prodti~ad.
F~~a p Q i 3.* Sis~"+3yeiz ~srara.r.3'~i Sii The catalyst was prepared using the methods described in Example 1. 2-Methylindole, (2.59 grams) from Aldrich Chemi.ca]. Ccmpaay and used without further purification, was p1acvd in a 23o ms3. Schlenlt. f1mslt wh3.04 conir-airiq~gn a~tirr~n~

bar. The flask was sealed with a sep}~: D?et-hyI athcr (70 m3) xaa a2Lcted by dovbYa-=r,d~o1 r,~1~ ima ~--metlhj ? i.rdel! _ Met-yl=s}?e-a.a.um karQmiae ~ +~ . i u ~, .~ 0 =Idx j 118p= 4 1r. ethar wras placed in ~(4 oz. bQtt1e ~nct 40 ~ a~' dia'el~.y~.

ether ;:as adda:d to dissolve it.

'Lthe 26-metbylindo1a soluticn :ra, ^c~oled i *! an i cQ bath at 0 C. The =ethyZmagnesium brc,mide so3.Tsticsn was added to the indole with a double-exded needle over 25 iu.:i.nutes _ Gas ~
2.5 AMENDED SHEET

FEB-2S-57 10:02 FROM=OXY PATENT CA 02208100 1997-06-18:71628E324s PACE 17/2"-~ evOlved durimq this addition. The reaction mixture was stirrred for 30 minutes at 06G. The ice bath was reraoved and thf-:' neiarture wa,rmed to raom temperature o~er 9 O minutes.
Thi.s praduct was stored overnight at io C.

Titanium tetra.chl.aride (1.10 ml) was placed in a dry, (ISML.
10, oxygen-free.,(4 oz.) bottle which contained a stirring bar.
-To2uene (40 ml) w-aS added to the bottle which was t zen sealed with a septum. The Schienk flask containing the reaction product of 2-m.ethylindolg and methy],magnesium bromide was cooled to a C in an ice bath. ior 15 mi.nutes.
The T:.C34 ~o-lution uas adtiari via do~Lt.b'Le-exded neecie over at=:xt +0. m~It.:.t2.s whjile st7.rri.ny. i-'he rrmGtion mixture was --atirrOd ~or a7aout 2.S htsurs eet 4 a. The ice bath was then removed and the mi.xtzire a.I.IQwe..d to wax-m to room temperature while stirriag. The flask was storAc3 at 1Oar otrer n igh t.

2 0 The Product was a reddish-black ~''~`~ t.~s~i 'w:a-b ~Ã~c+3is~3 ~~om tua siurry 1~~s ~vaporation vacuum. 'I''sse s~roeiu~~ was ~ b3eok s-i ld-AgProxiMateltr 100 mi of toluene was ad~.ed to th; s s:^o id a=~d stirred for one uL'ur ..~t room tGmpCCi=~. T`iJ.b r:dZiiii..'-A:l i-1 2-5 4i raYaL1Lsh ble~..ak :rii-`:L(wS ai.rYQ .iiiMPrGV VLL Ub1iig a fine fritted filter a-nd the solution was colZact&+3.. The taluer e was rQ.mavad by evaporation under -vac::u.sum giving a .
wC4r Ti.
- 2s -AMENDED SHEET

Polymerization Testing A solution of the product was prepared by dissolving 0.4501 grams in 100 ml of toluene. Polymerizations were conducted as described in Example 1, except that 10.0 ml of 10% MAO in toluene was added as a cocatalyst and the polymerization was conducted at 80 C with 3.0 moles of hydrogen added. Three ml of the catalyst,solution was used to start a polymerization and 12.5 grams of polymer was produced after one hour. The polymer had a MI of 0.048 dg/min and a HLMI of 3.04 dg/min. This corresponds to a MFR of 63.2.

Example 12 The polymerization described in Example 11 was repeated except that the amount of catalyst used was 1.5 ml of catalyst solution and 180 millimoles of hydrogen were added to the reactor. In one hour 14.4 grams of polymer was produced. The polymer had a MI of 0.393 dg/min and a HLMI of 7.78 dg/min. This corresponds to a MFR of 19.8.

Example 13 Catalyst Preparation The catalyst was prepared using the methods described in Example 1. 2-Methylindole (2.69 grams) from Aldrich Chemical Company and used without further purification, was FEB-25-97 10:03 FROM:OXY PATEhCA 02208100 1997-06-1810:7162863249 PAGE 18/2 placed in a 250 m1. Sclzlenk flask which contained a stirring bar. The flask was sealed with a septum. Diethyl et.her (40 nt].) was added by dc-ubie-ended needle to dissolve the 2-3nethyl indole . Methylmagnesium bromide (6.70 ml,, 3-o m,o I. ar ) 119"
in ether was placed in h(4 oz.) bottle and 3o m1 of diethyl ether was added to dissolve it.

The 2 methylinc3,ole solution was cooled in an ice bath at 0 C. The methylmagnesium bromide solution was added to the indole with a double-ended needle over I0 minutes. Gas PvolvPd duri.*:g this additicn- The reao`ion was stirred for 2 hours at- 0 C. The ice bath was removed and the mixture vas storec3. c-vernigIYt at 2o4c.

Zircxonium tetrachlori.da (2.30 grata) was placed in a aoh'! c-n-Ã f? -~msk which r's:T!t~ i?vCrl a stirrsrrl beLr. biet.hyl eather (12tT m1) was aadad and t,,'~s flatik war. caalad with aaaptum. The fJ"Las' w~.s stirred =or ww'v uo~ir m .i t L csSiC LC~ratLtZ,= aliQ LaC21 qQ2,Lc= ir-o Q` o in an ice bath.

Tho reacti.ott produat of 2-methylindole and methylm.agnesitum bromide was added to the ZrC14 slurry via 25 do+uble-cndcd needle over about zo minute--~ tir*3.iie stirrIng-Tbii DtOGZL1oLr.d a- ST&3.IeL7 r1.tiY'-"y e.Tj&Ie3s vas i~Yi']taa ~ar Ewv Ih:::=.:r= at Y ^ _ i4A bath w~r. rQ2-a-ved and a.llowaci t~o warm to rocba temperature whilft st=rrine3. T'rie G~,.~r wa~ r~~v~ ~rc~ titG Ziuri.-y s+y evagc?rctt=s~:z under AMENOtb ^~'EETj vacuum. Toluene (100 ml) was added to this solid and stirred for three hours at room temperature which resulted in a reddish slurry. The solids were filtered off using a fine fritted filter. The product was recovered from the toluene solution by evaporating the toluene under vacuum.
The product was a dark red solid which contained 12.2 wt%
Zr.

Polymerization Testing A solution of the product was prepared by dissolving 0.3440 grams in 100 ml of toluene. Polymerizations were conducted as described in Example 1, except that 10.0 ml of 10% MAO in toluene was added as a cocatalyst and the polymerization was conducted at 80 C with 120 millimoles of hydrogen added. Five ml of the catalyst solution was used to start a polymerization and 11.1 grams of polymer was produced after one hour. The polymer had a MI of 0.082 dg/min and a HLMI of 4.51 dg/min. This corresponds to a MFR of 54.8.

Example 14 This examples shows the effect of increased hydrogen on the catalyst activity. The polymerization described in Exampfe 13 was repeated except that 180 millimoles of hydrogen were added to the reactor. The amount of polymer produced in 1 hour was 7.3 grams. The polymer had a MI of 0.071 dg/min and a HLMI of 2.90 dg/min. This corresponds to a MFR of 41Ø

Example 15 This examples shows the effect of, hydrogen and 1-butene on the catalyst activity. The polymerization described in Example 13 was repeated except that 120 millimoles of hydrogen and 20 ml of liquid 1-butene were added to the reactor. The amount of polymer produced in 1 hour was 8.5 grams. The polymer had a HLMI of 1.05 dg/min.
Example 16 Carbazole (1.67 grams, from Aldrich Chemical Company) was recrystallized from ether and was placed in a 250-mL
Schlenk flask which contained a stirring bar. The flask was sealed with a septum. Ether (100 mL) was added by double-ended needle. The solution was cooled to 0 C in an ice bath. Methylmagnesium bromide (3.30 mL, 3.0 molar) in ether (from Aldrich Chemical Company) was added slowly by syringe while stirring. Gas evolved during this addition.
The reaction mixture was stirred for one hour. The ice bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional one hour at room temperature.

Zirconium tetrachloride (1.16 grams) from Aldrich Chemical Company (used without further purification) was placed in a clean, dry, oxygen-free 250-mL Schlenk flask which contained a stirring bar. The flask was sealed with a septum. 50 mL of ether was added by double-ended needle.
This suspension was cooled to -78 C in a dry ice/isopropanol bath. The carbazole/methylmagnesium bromide product was added to the ZrCl4 suspension over ten minutes using a double-ended needle. The reaction mixture was stirred for one hour. The bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional hour at room temperature. The product was a yellow-orange slurry.

The ether was removed from the slurry by evaporation under vacuum. Toluene (100 mL) was added to this solid and stirred for two hours at room temperature. The solution was recovered by vacuum filtration using a fine (4 micron) fritted glass filter. The toluene was removed by evaporation under vacuum. The product was a green solid which contained 8.1 wt% Zr.

Polymerization Results Polymerizations were conducted in a stirred 1.7 liter stainless steel autoclave at 80 C. Dry, oxygen-free toluene (840 mL) was charged to the clean, dry, oxygen-free reactor and 6.0 mL of 10% methylaluminoxane (MAO) in toluene (from Ethyl Corporation and used without further purification) was added to the toluene in the reactor. No hydrogen or comonomer were added to the reactor. Sufficient ethylene was added to bring the reactor pressure to 15C) psig. A
solution of catalyst was prepared by dissolving 0.1090 grams of product in 100 mL of toluene. , A polymerization was started by injecting 1.0 mL of this solutiori.

At the end of one hour the ethylene flow was stopped and the reactor rapidly cooled to room temperature. The polymer was filtered from the toluene by vacuum filtration.
It was dried overnight in a vacuum oven and weighed. The weight of the polymer was 26.8 grams. This corre:sponded to a catalyst productivity of 304 kg/g Zr. The polymer had a MI of 0.136 dg/min and HLMI of 1.30 dg/min. This corresponds to a MFR of 9.6. This indicates a narrow molecular weight distribution even though the molecular weight was high.

Examnle 17 The catalyst described in Example 16 was tested under the same polymerization conditions as Example 16 except that 25 mL of the catalyst solution was diluted to 100 mL
with toluene. This diluted solution (1.0 mL) weis used under the same conditions as Example 16. A one hour polymerization resulted in 38.3 grams of polyethylene.
This corresponded to a catalyst productivity of 1,737 kg/g Zr. The polymer had a MI of 0.142 dg/min and HLMI of 1.45 dg/min. This corresponds to a MFR of 10.2. The polymer density was 0.9599 g/mL.

Example 18 The catalyst described in Example 16 was tested under the same polymerization conditions as in Example 17 except that 20 mL of 10-butene was added as a comonomer. The 41.0 grams of polyethylene produced corresponded to a catalyst productivity of 1,859 kg/g Zr. The polymer had a MI of 0.154 dg/min and HLMI of 1.71 dg/min. This corresponds to a MFR of 11.1. The polymer density was 0.9411 g/mL.

Example 19 The catalyst described in Example 16 was tested under the same polymerization conditions as in Example 17 except that 30 mmoles of hydrogen was added to the reactor. The 7.8 grams of polyethylene produced corresponded to a .20 catalyst productivity of 354 kg/g Zr. The polymer had a MI
of 197 dg/min. The polymer density was greater than 0.9700 g/mL.

Example 20 Catalyst Preparation The catalyst was prepared using the methods described in Example 16 except that 5.0 mL of a 1.0 molar solution of TiCl4 in toluene was used in place of ZrCl4. The product was a black solid which contained 8.7 wt% Ti.

Polymerization Testing - , A solution of the product was prepared by dissolving 0.1065 grams in 100 mL of toluene. Polymerizations were conducted as described in Example 16. A polymerization was started using 1.0 mL of the catalyst solution and 18.1 grams of polymer was produced after one hour. This corresponded to a catalyst productivity of 196 kg/g Ti.
The polymer had a MI of 0.150 dg/min and a HLMI of 1.60 dg/min. This corresponds to a MFR of 10.7.

Example 21 The catalyst described in Example 20 was tested under the same polymerization conditions as Example 16 except that 25 mL of the catalyst solution was diluted to 100 mL

with toluene. 1.0 mL of this diluted solution was used under the same conditions as Example 17. A one hour polymerization resulted in 10.0 grams of polyethylene.
This corresponded to a catalyst productivity of 432 kg/g Ti. The polymer had a MI of 0.200 dg/min and HLMI of 1.64 dg/min. This corresponds to a MFR of 8.2.

Example 22 The following example demonstrates the preparation of bis(carbazolyl)zirconium dichioride by the method of reacting tetrakis(diethylamido)zirconium with carbazole followed by chlorination with silicon tetrachloride.

Catalyst Preparation All steps were conducted under an argon atmosphere using conventional Schlenk-line techniques. All glassware was clean and free of moisture and oxygen. All solvents were freed of water, air, and other impurities.

Carbazole (1.874 grams from Aldrich Chemical Company) was added at room temperature to a solution of 2.0 grams of tetrakis(diethylamido) zirconium dissolved in 40 ml of toluene. This was added over a ten minute period and stirred for three hours at room temperature. The volatiles were removed under vacuum. The resulting residue was dissolved in 30 mis of toluene. Silicon tetrachloride (0.954 grams) in 5:0 ml of toluene was added at room temperature. The mixture was stirred for four hours at room temperature. At the end of this period a greenish-yellow solid had separated from the initially brown solution. By evaporating the volatiles, 1.43 grams of solid was recovered. This was used without further purification.

Polymerization Results Polymerizations were conducted in a stirred 1.7 liter stainless steel autoclave at 80 C. Dry, oxygen-free toluene (840 ml) was charged to the clean, dry, oxygen-free reactor. Six ml of 10t methylaluminoxane (MAO) in toluene (from Albemarle Corporation and used withou=t further purification) was added to the toluene in the reactor. No hydrogen or comonomer were added. Sufficient ethylene was added to bring the reactor pressure to 150 psig. A

solution of catalyst was prepared by dissolving 0.2508 grams of product in 100 ml of toluene. To start a polymerization 2.0 ml of this solution was injected into the reactor. At the end of one hour the ethylene flow was stopped and the reactor rapidly cooled to room temperature.

The polymer was filtered from the toluene by vacuum filtration. It was dried overnight in a vacuum oven and weighed. The weight of the polymer was 9.1 grams. This corresponded to a catalyst productivity of 9.88 kg/g Zr.
The polymer had a MI of 0.060 dg/min and HLMI of 0.36 dg/min. This corresponds to a MFR of 6.0 and indicates a narrow molecular weight distribution, even though the molecular weight was very high.

Example 23 The catalyst described in Example 22 was tested under the same polymerization conditions as Example 22 except WO 96%20223 PCT/US95/16942 that 4.0 ml of the catalyst solution was used. A one hour polymerization resulted in 9.3 grams of polyethylene. This corresponded to a catalyst productivity of 5.05 kg/g Zr.
The polymer had a MI of 0.0031 dg/min and HLMI of 0.097 dg/min. This corresponds to a MFR of 31.4.

Comparative Example 1 Catalyst Prenaration The catalyst was prepared using the methods described in Example 1. Pyrrole (from Aldrich Chemical Company) was distilled under nitrogen. Pyrrole (1.40 ml, 1.36 grams) was placed in a 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum. Diethyl ether (50 ml) was added by double-ended needle to dissolve the pyrrole. The solution was cooled to 0 C in an ice bath and 6.70 ml of 3.0 molar methylmagnesium bromide in ether was added slowly by syringe while stirring. Gas evolved during this addition. The reaction mixture was stirred for 1 hour. The ice bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional 1 hour at room temperature.

Zirconium tetrachloride (2.33 g) was placed in a clean, dry oxygen-free 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum and 100 ml of ether was added by double-ended needle. This suspension was cooled to 0 C in an ice bath. The pyrrole/methylmagnesium bromide product was added to the ZrC14 suspension over 10 minutes using a double-ended needle. The reaction mixture was stirred for 1 hour. The ice bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional hour at room temperature. The product was a yellow slurry.

The ether was removed from the slurry by evaporation under vacuum. This produced a brown solid. 100 ml of toluene was added to this solid and stirred for 2 hours at room temperature. The solution was recovered by vacuum filtration using a fine (4 micron) fritted glass filter.

The toluene was removed by evaporation under vacuum. The amount of solid recovered was 0.453 g and it contained 15.1% Zr. Elemental analysis did not show the presence of C1.

Polymerization Testing A solution of the product was prepared by dissolving 0.3201 grams in 100 ml of toluene. Polymerizations were conducted as described in Example 1, except the 6.0 ml of 10% MAO in toluene was added as a cocatalyst and the polymerization was conducted at 110 C. No hydrogen or FES-25-97 10 = 03 FROM : OXY PATEId'CAu~ YARTMEAIT 97 06 18D _71E26S3249 PAGE 19/2' ~ comoriomer were added to the reaotor. Five MZ of the catalyst solutivn was used to start a polymerization and 24.3 grams of polymer was produced after one hour.. The polymer had a MI of 1.20 dg/min and a HLMI of 27.85 dg/min._ This corresponds to a MM of 23.2.

ng=-rativE* EX.'a=le 2 This example shows the low catalyst yield and low polymerization activities which rpsstl.t from Ztsing py='role derivatives which do not have aromatic ringo fused to the 17yrrole ring.

Dry, oxygen-free 2, 5-di;aethylpy 3: roltt~ (1.00 y rns, 9q+-*, f~om: Aldrich Chemtc.al company) wms p3.acad yn a cl e-a-*
lLBAL
dry, oxygest-free^(4 ounce) bottle with a stir bar and sealed with a rubber septum. Ether (50 ml) was added by syringe.
The solution was cooled to o C in an ice bath.

14iat2Zylma.gn.esisim brants.do (4.7 mI af 3_ O mo? ar) ethe?'`' (froat A].dd~C3:ch MermiGal Company) was placed i..n a separate 4 ounoe bottle and dissolved in 50 ml of ether_ This methylmac3rtesium bromide/ether solution was slowly added to the 2,5--d3methy 'u~' ' _n using .idr?u..nrt-~ci.~t~
~.Pyrroie :~c~~~:~..1.^' .

nOedlg wYriile stirr33zg. faaa e:sso3.v~2 dxii-snzi thi~ ~dalitl0172:
ren~ ~. :.,f~, Th~ r&istti~ra was stirred ft~r 1 YiOUe. tu+~ s_i-~., L~'+v. ~..s~
-SKET

was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional 1 hour at room temperature.

Zirconium tetrachloride (2.32 grams, from Aldrich Chemical Company and used without further purification) was placed in a clean, dry, oxygen-free 250 ml Schlenk flask which contained a stirring bar. The flask was sealed with a septum and 70 ml of dry, oxygen-free ether was added by syringe. This solution was cooled to 0 C in an ice bath.

The 2,5-dimethylpyrrole/methylmagnesium bromide product was added to the ZrC14 slurry over 10 minutes using a double-ended needle. The reaction mixture was stirred for about 2 hours. The bath was removed and the mixture was allowed to warm to room temperature while stirring. The mixture was stirred an additional hour at room temperature. The ether was evaporated and a tan solid product was recovered.
Toluene (100 ml) was added to this solid and stirred for 3 hours at room temperature. The solution was recovered by vacuum filtration using a fine (4 micron) fritted glass filter. The dissolved product was precipitated from solution by the addition of 700 ml of hexane. The solids were recovered by vacuum filtration using a fine fritted glass filter. Approximately 0.06 gram of light yellow solid was produced.

FEB-2S-B7 10:03 FROM:OXY PATEIv4~A 022081001997-06-18tD,7162663249 PAGE 20/2^
pc~1 y m~r; r ~ QIt F~~L~ t5 Polymerizations were conducted using the procedure described in Example 1. In this example, =10.0 m]. of 10%
methylaluminoxane (MAO) in toluene (from Eth.y3. Corporation and used without further purification) was added to the toluene in the reactor. Hyd.rogen (1$0 mmoles) ancl no comonomer were added to the reactor. A solution of catalyst was prepared by dissolving 0.050 grams of. product in 100 mi of toluene. Three ml of this solution was Injected into the ?"eact-or '~v sraLrt a Ao,'I.S7ma7Cizat3.oE1 arau ` . v is grams of polymer was produCed.

r,nmnaZ:a _ i v¾ Exampl e 3 Distilled pyrrole t1.38 mi, from A?drich chemic:al Ccrmpanyj was placed in aW.aan, d~:,~, . Y~ys.-Ãrea 2-9*~ -ml sc3a.lenk flask with a stir bar and sealed with a rubber sep'G1=a Lt2].8r (40 Ial.) waa Ctdd=d 1:'y cSyringe. iiiseN c~alu~.i.aiz was cooled to o'C in an ice bath and 6.7 ud_ of 3.0 malar 3a.athylmagnasizim bromide in ether (from Aldrich ciaemi.oa'L
Compsa.y) was pZa.oad in aH~4 au.. 7ce) b0tt3s and dissraive3. in 40 ml oà etFx.er. Thia 1t*thyima.gne83.UM

was slowly added to the pyrrole solution using a d.ouble-ended needle while stirring. Gas evolved during this addition. The reacti.oxl mi~u~=e was ati'rr~a. ior 1 J'Ao`.~r .

AMENDED SHEET

FE2-25-97 10 = 04 FROM = OXY PATENCA 02208100 1997-06- 181 Lj , 7162e63249 PAOE 21/2"

The ice bath was removed and the mixture was allowed to warm to roam temgerature while stirring. The mixture was stirred an additional 1 hour at room temperature.

Tit.azxiubt tetrachloride (1_10 ml, from Aldrich Chemical Coatpany) waLs dissolved in 30 ml of toluene in a clean, dry, oxygen-free ~4 ounae)hottle which contained a stirring bar.

The bottle was sealed with a septum. The TiC14 solution was added to the pyrrole/methy3magnesium bromide product at 0 C
over 20 minutes using a doubie-ended needle. The reaction mixt~.tra was stirred for about 2 hours. The ice bath was rezaovecl and the mixture was al ? owed to warm to room testp$r&ttsr* u1xi1a r_tI.rring_ 7`he mix--txre was stirred aii add%ty..csn&1 hossr at rc~om temp4Qrature_ The ether was evaporated a.nd a dark brown solid was recovered.

s tirr ad Toluene (100 ml) was added to tkkis solid and bLozL. s at room temr-erata3r+3. `?n¾ solution Wa5 reoovared by vacu~ fi2tration using a fritt~d ariass =ilter. Tho clissol.vad product was recovered by evaporating Polvrjneri zati ort Re~~~

?olymerizations were condo.cted using the procedure described in Example i except that met?iyl a? utti-nQxana 04AO) irz toluene was adcle.d to tue rea.4 tor along with 180 mmoles of hydrogen, but no oomQn.omer. A

AMENDED SHEET

solution of catalyst was prepared by dissolving 0.0960 grams of product in 100 ml of toluene. Three ml of this solution was injected into the reactor to start a polymerization and 3.4 grams of polymer was produced over one hour.

Claims

WE CLAIM:

1. A catalyst composition comprising a cocatalyst and a catalyst having the general formula where L is a ligand, or mixture of ligands, each having 4 to 30 carbon atoms and containing at least two fused rings, one of which is a pyrrolyl ring and the other of which is aromatic, Cp is a ligand containing a cyclopentadienyl group, where two L ligands or an L and a Cp ligand can be bonded to each other via a bridging group, B is a Lewis base, Y is selected from the group consisting of halogen, alkoxy from C1 to C20, siloxy (R1)3SiO-, N(R1)2, and mixtures thereof, M is selected from the group consisting of titanium, zirconium, and mixtures thereof, R1 is alkyl from C1 to C20, m is 2 to 4, n is 0 or 1, p is 0 or 1, q is 0 or 1, m + n + q = 4, and m + q is 3 or 4.

2. A catalyst composition according to claim 23 wherein M is titanium.

3. A catalyst composition according to claim 23 wherein M is zirconium.

4. A catalyst according to Claim 1 wherein Y is halogen.

5. A catalyst according to Claim 4 wherein Y is chlorine.

6. A catalyst according to Claim 1 wherein L is indolyl or substituted indolyl and has the formula where each R is independently selected from hydrogen, alkyl from C1 to C10 and aryl from C6 to C10 and 5 is 1 to 4.

7. A catalyst according to Claim 1 wherein L is carbazolyl or substituted carbazolyl and has the formula where each R is independently selected from hydrogen, alkyl from C1 to C10, and aryl from C6 to C10 and ~ is 1 to 4.

8. A catalyst according to C1aim 1 wherein m is 3.

9. A catalyst according to Claim 1 wherein m is 4.

10. A catalyst according to Claim 1 in combination with an organometallic cocatalyst.

11. A catalyst according to Claim 10 wherein said organometallic cocatalyst is an aluminoxane.

22. A catalyst according to Claim 10 in combination with one or more monomers polymerizable therewith.

13. A catalyst according to Claim 12 wherein said monomer is ethylene.

14. A method of polymerizing an unsaturated olefinic monomer comprising contacting said monomer with the catalyst according to Claim 10.

15. A catalyst comprising a metal ligand having the general formula where L is a ligand containing an indolyl or carbazolyl group, M is selected from the group consisting of titanium, zirconium, and mixtures thereof, X is halogen, and m is 2, 3, or 4.

16. A catalyst according to Claim 15 wherein M is titanium.

17. A catalyst according to Claim 15 wherein M is zirconium.

18. A catalyst according to Claim 15 wherein X is chlorine.

19. A catalyst according to Claim 15 wherein m is 3.

20. A catalyst according to claim 15 wherein m is 4.

23. A catalyst composition according to Claim 1 wherein said cocatalyst contains aluminoxane or an aluminum alkyl.

24. A catalyst composition comprising a cocatalyst containing methylaluminoxane and a catalyst comprising a compound having the general formula [L]m - Zr - [X]4-n where L is a ligand, or mixture of ligands, each having 4 to 30 carbon atoms and containing at least two fused rings, one of which is a pyrrolyl ring and the other of which is aromatic, where two L ligands can be bonded to each other via a bridging group, X is halogen, and m is 3 or 4.

25. A catalyst composition according to Claim 24 wherein m is 3.

26. A catalyst composition according to Claim 24 wherein m is 4.

27. A catalyst composition comprising a cocatalyst containing methylaluminoxane and a catalyst having the general formula [L]4 - Zr where L is carbazolyl or indolyl with a C1 to C4 alkyl in the 2 position, in the 7 position, or in both the 2 and 7 positions.
CA002208100A 1994-12-19 1995-12-18 Azametallocene polymerization catalysts Abandoned CA2208100A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/358,492 US5539124A (en) 1994-12-19 1994-12-19 Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring
US358,492 1994-12-19

Publications (1)

Publication Number Publication Date
CA2208100A1 true CA2208100A1 (en) 1996-07-04

Family

ID=23409865

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002208100A Abandoned CA2208100A1 (en) 1994-12-19 1995-12-18 Azametallocene polymerization catalysts

Country Status (13)

Country Link
US (1) US5539124A (en)
EP (1) EP0799250B1 (en)
JP (1) JPH11507084A (en)
CN (1) CN1173186A (en)
AU (1) AU4609896A (en)
BR (1) BR9510288A (en)
CA (1) CA2208100A1 (en)
DE (1) DE69520450T2 (en)
ES (1) ES2157355T3 (en)
FI (1) FI973660A0 (en)
RU (1) RU2164228C2 (en)
TW (1) TW413685B (en)
WO (1) WO1996020223A2 (en)

Families Citing this family (183)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5631202A (en) 1993-09-24 1997-05-20 Montell Technology Company B.V. Stereospecific metallocene catalysts with stereolocking α-CP substituents
TW330217B (en) 1994-12-20 1998-04-21 Kimberly Clark Co Low gauge films and film/nonwoven laminates
ZA9510604B (en) 1994-12-20 1996-07-03 Kimberly Clark Co Low gauge films and film/nonwoven laminates
US6309736B1 (en) 1994-12-20 2001-10-30 Kimberly-Clark Worldwide, Inc. Low gauge films and film/nonwoven laminates
US6419966B1 (en) 1994-12-22 2002-07-16 Exxonmobil Chemical Patents Inc. Polyethylene articles with improved resistance to water vapor transmission
US20030199657A1 (en) * 1994-12-22 2003-10-23 Davis Donna Sue Polyethylene articles with improved resistance to water vapor transmission
US6403772B1 (en) * 1995-09-11 2002-06-11 Montell Technology Company, Bv Open-pentadienyl metallocenes, precursors thereof and polymerization catalysts therefrom
ID22443A (en) * 1996-11-15 1999-10-14 Montelll Technology Co Bv HETEROSICLIC METALLOSENA AND CATALYST POLYMERIZATION
US6451938B1 (en) 1997-02-25 2002-09-17 Exxon Mobil Chemical Patents Inc. Polymerization catalyst system comprising heterocyclic fused cyclopentadienide ligands
US6410664B1 (en) 1997-03-24 2002-06-25 Cryovac, Inc. Catalyst compositions and processes for olefin polymers and copolymers
US6573345B1 (en) 1997-03-24 2003-06-03 Cryovac, Inc. Catalyst compositions and processes for olefin oligomerization and polymerization
US6160072A (en) * 1997-05-02 2000-12-12 Ewen; John A. Process for polymerizing tactioselective polyolefins in condensed phase using titanocenes
DE19728126A1 (en) * 1997-07-02 1999-01-07 Bayer Ag Catalyst system based on monoazadiene metal complexes
US6045900A (en) 1997-09-15 2000-04-04 Kimberly-Clark Worldwide, Inc. Breathable filled film laminate
US6096668A (en) * 1997-09-15 2000-08-01 Kimberly-Clark Worldwide, Inc. Elastic film laminates
US6245868B1 (en) 1998-05-29 2001-06-12 Univation Technologies Catalyst delivery method, a catalyst feeder and their use in a polymerization process
US5914408A (en) * 1998-08-07 1999-06-22 Equistar Chemicals, Lp Olefin polymerization catalysts containing benzothiazole
US6008394A (en) * 1998-08-07 1999-12-28 Arco Chemicals Technology, L.P. Sulfonyl catalysts and method of using the same
US6114270A (en) * 1998-08-07 2000-09-05 Equistar Chemicals, L.P. Polymerization-stable anionic ancillary ligand containing alkylimido catalysts and method of using the same
US6121181A (en) * 1998-08-07 2000-09-19 Equistar Chemicals, L.P. Cyclic oligomeric oxo- and imido- metal complexes as olefin polymerization catalysts
US6454989B1 (en) 1998-11-12 2002-09-24 Kimberly-Clark Worldwide, Inc. Process of making a crimped multicomponent fiber web
US6723669B1 (en) * 1999-12-17 2004-04-20 Kimberly-Clark Worldwide, Inc. Fine multicomponent fiber webs and laminates thereof
KR100295601B1 (en) * 1999-01-18 2001-07-03 박찬구 Process for selective hydrogenation of conjugated diene polymer
US6506704B1 (en) 1999-03-23 2003-01-14 Cryovac, Inc. Olefin polymerization catalysts and processes for making and using same
US6180552B1 (en) 1999-04-07 2001-01-30 Equistar Chemicals, L.P. Transition metal complexes containing neutral, multidentate azacyclic ligands
US6204216B1 (en) 1999-04-15 2001-03-20 Equistar Chemicals, L.P. Olefin polymerization catalysts containing amine derivatives
US6201076B1 (en) 1999-04-29 2001-03-13 Equistar Chemicals, L.P. Olefin polymerization process with fatty amine additives for improved activity and reduced fouling
US6127484A (en) * 1999-04-29 2000-10-03 Equistar Chemicals, Lp Olefin polymerization process
US6020493A (en) * 1999-05-06 2000-02-01 Equistar Chemicals, Lp Single-site catalyst preparation
US6291386B1 (en) * 1999-05-25 2001-09-18 Equistar Chemicals, Lp Process for the in-situ preparation of single-site transition metal catalysts and polymerization process
US6211311B1 (en) * 1999-05-25 2001-04-03 Equistar Chemicals, L.P. Supported olefin polymerization catalysts
MXPA02000366A (en) * 1999-07-28 2002-07-02 Kimberly Clark Co Cd extensible clothlike nonwoven for facing and liner.
US6239062B1 (en) 1999-09-02 2001-05-29 Equistar Chemicals, L.P. Olefin polymerization catalysts containing indolyl-amido ligands
US6194527B1 (en) 1999-09-22 2001-02-27 Equistar Chemicals, L.P. Process for making polyolefins
US6613704B1 (en) * 1999-10-13 2003-09-02 Kimberly-Clark Worldwide, Inc. Continuous filament composite nonwoven webs
US6777056B1 (en) 1999-10-13 2004-08-17 Kimberly-Clark Worldwide, Inc. Regionally distinct nonwoven webs
US6232260B1 (en) 1999-10-14 2001-05-15 Equistar Chemicals, L.P. Single-site catalysts for olefin polymerization
US6228959B1 (en) 1999-10-15 2001-05-08 Equistar Chemicals, L.P. Single-site catalysts containing homoaromatic ligands
US6479154B1 (en) 1999-11-01 2002-11-12 Kimberly-Clark Worldwide, Inc. Coextruded, elastomeric breathable films, process for making same and articles made therefrom
US6794024B1 (en) 1999-11-01 2004-09-21 Kimberly-Clark Worldwide, Inc. Styrenic block copolymer breathable elastomeric films
US6294626B1 (en) 1999-11-15 2001-09-25 Equistar Chemicals, Lp Olefin polymerization catalysts containing modified boraaryl ligands
US6281155B1 (en) 1999-11-19 2001-08-28 Equistar Chemicals, L.P. Supported olefin polymerization catalysts
US6281306B1 (en) 1999-12-16 2001-08-28 Univation Technologies, Llc Method of polymerization
US6239239B1 (en) 2000-02-17 2001-05-29 Equistar Chemicals, L.P. Quinolinoxy and pyridinoxy single-site catalysts containing benzyl ligands
US6255415B1 (en) * 2000-02-29 2001-07-03 Equistar Chemicals, L.P. Ethylene polymerization process
US6476165B1 (en) 2000-03-08 2002-11-05 Equistar Chemicals, Lp Olefin polymerization process using fatty amine additives and boron-modified supported catalyst
US6498221B1 (en) * 2000-03-30 2002-12-24 Equistar Chemicals, Lp Single-site catalysts containing chelating N-oxide ligands
US6812304B2 (en) 2000-06-14 2004-11-02 Equistar Chemicals, Lp Process for producing improved premixed supported boraaryl catalysts
US6433088B1 (en) 2000-08-04 2002-08-13 Equistar Chemicals, Lp Clear and printable polypropylene films
US6486270B1 (en) 2000-08-25 2002-11-26 Equistar Chemicals, Lp High molecular weight, medium density polyethylene
US6355733B1 (en) 2000-10-13 2002-03-12 Equistar Chemicals, Lp Polyethylene blends and films
US6414099B1 (en) 2000-10-18 2002-07-02 Equistar Chemicals, Lp Single-site catalysts based on caged diimide ligands
US6982231B1 (en) 2000-10-27 2006-01-03 Kimberly-Clark Worldwide, Inc. Elastomeric, breathable laminate with enhanced breathability upon extension
US6660678B1 (en) * 2000-11-21 2003-12-09 Equistar Chemicals, Lp Single-site catalysts for olefin polymerization
US6582810B2 (en) 2000-12-22 2003-06-24 Kimberly-Clark Worldwide, Inc. One-step method of producing an elastic, breathable film structure
US6673882B2 (en) * 2001-02-12 2004-01-06 Equistar Chemicals, Lp Supported single-site catalysts useful for olefin polymerization
US6664349B2 (en) 2001-03-29 2003-12-16 Equistar Chemicals, Lp Ethylene polymerization process
US6414162B1 (en) 2001-04-05 2002-07-02 Equistar Chemicals, Lp Bimetallic catalysts for olefin polymerization
US6579957B2 (en) 2001-04-11 2003-06-17 Equistar Chemicals, Lp Single-site catalysts based on anionic thiopyran dioxide ligands
US6391988B1 (en) 2001-04-18 2002-05-21 Equistar Chemicals L.P. Tris(pyrazoyl) based anions
US6583240B2 (en) * 2001-05-23 2003-06-24 Equistar Chemicals, Lp Ethylene polymerization process
US6759361B2 (en) 2001-06-04 2004-07-06 Equistar Chemicals, Lp Aluminoboronate activators for single-site olefin polymerization catalysts
US6489414B1 (en) * 2001-06-06 2002-12-03 Equistar Chemicals, Lp Chelating pyrimidines as ligands for single-site olefin polymerization catalysts
US6583242B2 (en) 2001-08-02 2003-06-24 Equistar Chemicals, Lp Supported olefin polymerization catalysts
US6562973B1 (en) 2001-08-15 2003-05-13 Equistar Chemicals, Lp Method for making late transition metal catalysts for olefin polymerization
US6455704B1 (en) * 2001-09-06 2002-09-24 Equistar Chemicals L.P. Process for the preparation of base-free carbazolide anions
US6586545B1 (en) 2001-12-20 2003-07-01 Equistar Chemicals, Lp Complexes based on four-membered cyclic anionic six-electron-donor ligands
US6596826B1 (en) 2001-12-20 2003-07-22 Equistar Chemicals, Lp Olefin polymerization catalysts containing 1,3-diboretanyl ligands
US6841504B2 (en) * 2002-01-28 2005-01-11 Univation Technologies, Llc Polymerization catalyst activator and its use in a polymerization process
US6613841B2 (en) 2002-01-28 2003-09-02 Equistar Chemicals, Lp Preparation of machine direction oriented polyethylene films
US6780807B2 (en) 2002-02-04 2004-08-24 Equistar Chemicals L.P. Acyclic anionic six-electron-donor ancillary ligands
US6689848B2 (en) 2002-03-04 2004-02-10 Equistar Chemicals, Lp Late transition metal polymerization catalysts
JP4576126B2 (en) * 2002-04-12 2010-11-04 ダウ グローバル テクノロジーズ インコーポレイティド Azaborolyl group 4 metal complex, catalyst and olefin polymerization method
US6908972B2 (en) 2002-04-16 2005-06-21 Equistar Chemicals, Lp Method for making polyolefins
US7094723B2 (en) * 2002-04-18 2006-08-22 Equistar Chemicals Lp Catalysts containing at least one heterocyclic ligand for improving the catalysts' performance of olefin polymerization
US6642326B1 (en) 2002-05-03 2003-11-04 Equistar Chemicals, Lp Use of silanes to enhance activity in single-site polymerizations
US6649698B1 (en) 2002-05-17 2003-11-18 Equistar Chemicals, Lp Polyethylene blends
US6630547B1 (en) 2002-06-11 2003-10-07 Equistar Chemicals, Lp Use of silanes to control molecular weight in olefin polymerizations
US20040002273A1 (en) * 2002-07-01 2004-01-01 Kimberly-Clark Worldwide, Inc. Liquid repellent nonwoven protective material
US6559251B1 (en) 2002-08-02 2003-05-06 Equistar Chemicals, Lp Process for making low-density polyolefins
US6896843B2 (en) * 2002-08-30 2005-05-24 Kimberly-Clark Worldwide, Inc. Method of making a web which is extensible in at least one direction
US6677038B1 (en) 2002-08-30 2004-01-13 Kimberly-Clark Worldwide, Inc. 3-dimensional fiber and a web made therefrom
US6881375B2 (en) * 2002-08-30 2005-04-19 Kimberly-Clark Worldwide, Inc. Method of forming a 3-dimensional fiber into a web
US6765074B2 (en) 2002-09-27 2004-07-20 Equistar Chemicals, Lp Olefin polymerization process
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
CA2499951C (en) 2002-10-15 2013-05-28 Peijun Jiang Multiple catalyst system for olefin polymerization and polymers produced therefrom
US6630548B1 (en) 2002-11-01 2003-10-07 Equistar Chemicals, Lp Static reduction
US20040102123A1 (en) * 2002-11-21 2004-05-27 Bowen Uyles Woodrow High strength uniformity nonwoven laminate and process therefor
US6989125B2 (en) * 2002-11-21 2006-01-24 Kimberly-Clark Worldwide, Inc. Process of making a nonwoven web
US6841500B2 (en) * 2002-12-03 2005-01-11 Equistar Chemicals, Lp Bimetallic indenoindolyl catalysts
US7666410B2 (en) 2002-12-20 2010-02-23 Kimberly-Clark Worldwide, Inc. Delivery system for functional compounds
US7582308B2 (en) * 2002-12-23 2009-09-01 Kimberly-Clark Worldwide, Inc. Odor control composition
US20040131836A1 (en) * 2003-01-02 2004-07-08 3M Innovative Properties Company Acoustic web
US20040231914A1 (en) * 2003-01-02 2004-11-25 3M Innovative Properties Company Low thickness sound absorptive multilayer composite
US7320739B2 (en) * 2003-01-02 2008-01-22 3M Innovative Properties Company Sound absorptive multilayer composite
US20040176241A1 (en) * 2003-03-04 2004-09-09 Sandor Nagy Benzoindenoindolyl metal catalysts for olefin polymerization
US6693155B1 (en) * 2003-03-05 2004-02-17 Equistar Chemicals, Lp Propylene polymerization process
WO2004094487A1 (en) 2003-03-21 2004-11-04 Dow Global Technologies, Inc. Morphology controlled olefin polymerization process
US6710005B1 (en) * 2003-04-10 2004-03-23 Equistar Chemicals, Lp Aluminoxane modification
US6812183B1 (en) * 2003-04-23 2004-11-02 Equistar Chemicals, Lp Triple-decker catalysts based on delocalized dianionic ligands
US6794468B1 (en) * 2003-05-12 2004-09-21 Equistar Chemicals, Lp Olefin polymerization process
US6995216B2 (en) * 2003-06-16 2006-02-07 Equistar Chemicals, Lp Process for manufacturing single-site polyolefins
US6818713B1 (en) 2003-08-11 2004-11-16 Equistar Chemicals, Lp Process for making polyethylene
US7932196B2 (en) 2003-08-22 2011-04-26 Kimberly-Clark Worldwide, Inc. Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications
US6939930B2 (en) 2003-09-09 2005-09-06 Equistar Chemicals, Lp Hydrosilane additives for increased polyolefin molecular weight
US7005489B2 (en) * 2003-09-29 2006-02-28 Equistar Chemicals, Lp Zwitterionic Metallocycles
US6958377B2 (en) * 2003-10-15 2005-10-25 Equistar Chemicals, Lp Olefin polymerization process
US7879350B2 (en) 2003-10-16 2011-02-01 Kimberly-Clark Worldwide, Inc. Method for reducing odor using colloidal nanoparticles
US7794737B2 (en) 2003-10-16 2010-09-14 Kimberly-Clark Worldwide, Inc. Odor absorbing extrudates
US7754197B2 (en) 2003-10-16 2010-07-13 Kimberly-Clark Worldwide, Inc. Method for reducing odor using coordinated polydentate compounds
US7438875B2 (en) 2003-10-16 2008-10-21 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified silica particles
US7837663B2 (en) 2003-10-16 2010-11-23 Kimberly-Clark Worldwide, Inc. Odor controlling article including a visual indicating device for monitoring odor absorption
US7678367B2 (en) 2003-10-16 2010-03-16 Kimberly-Clark Worldwide, Inc. Method for reducing odor using metal-modified particles
US7488520B2 (en) 2003-10-16 2009-02-10 Kimberly-Clark Worldwide, Inc. High surface area material blends for odor reduction, articles utilizing such blends and methods of using same
US7413550B2 (en) 2003-10-16 2008-08-19 Kimberly-Clark Worldwide, Inc. Visual indicating device for bad breath
US6930156B2 (en) * 2003-10-22 2005-08-16 Equistar Chemicals, Lp Polymer bound single-site catalysts
US20050118435A1 (en) * 2003-12-01 2005-06-02 Kimberly-Clark Worldwide, Inc. Films and methods of forming films having polyorganosiloxane enriched surface layers
US7326751B2 (en) * 2003-12-01 2008-02-05 Kimberly-Clark Worlwide, Inc. Method of thermally processing elastomeric compositions and elastomeric compositions with improved processability
US7985811B2 (en) * 2004-01-02 2011-07-26 Univation Technologies, Llc Method for controlling sheeting in gas phase reactors
US20070073012A1 (en) * 2005-09-28 2007-03-29 Pannell Richard B Method for seed bed treatment before a polymerization reaction
US20050148742A1 (en) * 2004-01-02 2005-07-07 Hagerty Robert O. Method for controlling sheeting in gas phase reactors
US6982305B2 (en) * 2004-01-26 2006-01-03 Equistar Chemicals, Lp Olefin polymerization in the presence of a dehydrogenation catalyst
US7011892B2 (en) * 2004-01-29 2006-03-14 Equistar Chemicals, Lp Preparation of polyethylene films
US20050175803A1 (en) * 2004-02-06 2005-08-11 D. Ryan Breese Preparation of polyethylene films
US20050200046A1 (en) * 2004-03-10 2005-09-15 Breese D. R. Machine-direction oriented multilayer films
PL1732756T3 (en) * 2004-04-05 2011-04-29 Leucadia Inc Degradable netting
US7175918B2 (en) * 2004-04-27 2007-02-13 Equistar Chemicals, Lp Polyolefin compositions
US8440125B2 (en) * 2004-06-28 2013-05-14 Equistar Chemicals, Lp Polyethylene films having high resistance to deformation or elongation
US20060003154A1 (en) * 2004-06-30 2006-01-05 Snowden Hue S Extruded thermoplastic articles with enhanced surface segregation of internal melt additive
US7285595B2 (en) * 2004-06-30 2007-10-23 Kimberly-Clark Worldwide, Inc. Synergistic fluorochemical treatment blend
US7125939B2 (en) * 2004-08-30 2006-10-24 Equistar Chemicals, Lp Olefin polymerization with polymer bound single-site catalysts
US7402546B2 (en) * 2004-09-23 2008-07-22 Equistar Chemicals, Lp Magnesium chloride support
US7500541B2 (en) 2004-09-30 2009-03-10 Kimberly-Clark Worldwide, Inc. Acoustic material with liquid repellency
WO2006065651A2 (en) 2004-12-17 2006-06-22 Dow Global Technologies Inc. Rheology modified polyethylene compositions
US20060177641A1 (en) * 2005-02-09 2006-08-10 Breese D R Multilayer polyethylene thin films
US8034461B2 (en) * 2005-02-09 2011-10-11 Equistar Chemicals, Lp Preparation of multilayer polyethylene thin films
US20060217490A1 (en) * 2005-03-22 2006-09-28 Lee Chun D Polyethylene compositions having improved printability
US7232604B2 (en) * 2005-07-28 2007-06-19 Equistar Chemicals, Lp Flame retardant crosslinkable compositions and articles
CN101326201B (en) * 2005-12-06 2011-11-02 巴塞尔聚烯烃意大利有限责任公司 Catalyst components for the polymerization of olefins
US20070141352A1 (en) 2005-12-15 2007-06-21 Calhoun Patricia H Cross-directional elastic films with machine direction stiffness
US7608327B2 (en) * 2005-12-20 2009-10-27 Equistar Chemicals, Lp High tear strength film
EP1803747A1 (en) 2005-12-30 2007-07-04 Borealis Technology Oy Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films
BRPI0706048A2 (en) 2006-05-02 2011-03-22 Dow Global Technologies Inc high density polyethylene composition, method for producing a high density polyethylene composition, article, bottle cap closure, method for improving bottle cap closures, and method for producing an article
US20070264512A1 (en) * 2006-05-11 2007-11-15 Mehta Sameer D Extrusion coating process for improved adhesion to metal(lized) substrates
US7456244B2 (en) * 2006-05-23 2008-11-25 Dow Global Technologies High-density polyethylene compositions and method of making the same
CN101096388B (en) * 2006-06-26 2010-05-12 中国石油天然气股份有限公司 Azole olefin polymerized catalyzer and preparation method and application thereof
US20080163978A1 (en) * 2007-01-09 2008-07-10 Botros Maged G Process for producing multi-layer structures having improved metal adhesion
US7399809B1 (en) 2007-01-11 2008-07-15 Equistar Chemicals, Lp Modifying polyethylene made by Ziegler or single-site catalyst with free radical initiator
US7794848B2 (en) * 2007-01-25 2010-09-14 Equistar Chemicals, Lp MDO multilayer polyethylene film
CN101245084B (en) 2007-02-14 2013-02-20 中国石油天然气股份有限公司 Substituted vinyl metallocene catalyst containing phosphine, preparation method and application thereof
ATE450569T1 (en) * 2007-05-02 2009-12-15 Dow Global Technologies Inc HIGH DENSITY POLYETHYLENE COMPOSITIONS, METHOD FOR PRODUCING THEREOF, INJECTION MOLDED ARTICLES MADE THEREFROM AND METHOD FOR PRODUCING SUCH ARTICLES
US7981517B2 (en) * 2007-08-28 2011-07-19 Dow Global Technologies Inc. Bituminous compositions and methods of making and using same
DE202008003190U1 (en) * 2008-01-04 2009-02-26 BLüCHER GMBH Functional protective material with reactively treated membrane and protective clothing produced therewith
US7544825B1 (en) 2008-06-12 2009-06-09 Basell Polyolefine Gmbh Preparation of siloxy-bridged metallocenes
WO2010056822A2 (en) * 2008-11-13 2010-05-20 Conwed Plastics Llc Oxo-biodegradable netting
EP2358767B1 (en) 2008-12-18 2013-02-20 Univation Technologies, LLC Method for seed bed treatment for a polymerization reaction
US9056970B2 (en) 2009-01-30 2015-06-16 Dow Global Technologies Llc High-density polyethylene compositions, method of producing the same, closure devices made therefrom, and method of making such closure devices
US20100239796A1 (en) * 2009-03-23 2010-09-23 Gagne Joseph Donald Lap sealable laminate and packaging made therefrom
EP2606096A1 (en) 2010-08-18 2013-06-26 Sun Chemical Corporation Chlorine-free ink and coating compositions&a method for printing on untreated polyolefin films with improved adhesion
US8895126B2 (en) 2010-12-31 2014-11-25 Kimberly-Clark Worldwide, Inc. Segmented films with high strength seams
CN104918947A (en) 2012-12-28 2015-09-16 尤尼威蒂恩技术有限责任公司 Methods for integrating aluminoxane production into catalyst production
CN105121015A (en) 2013-01-14 2015-12-02 尤尼威蒂恩技术有限责任公司 Methods for preparing catalyst systems with increased productivity
CN104558058B (en) * 2013-10-12 2017-08-08 中国科学院长春应用化学研究所 Metallocene complex and preparation method thereof, carbon monoxide-olefin polymeric
WO2016086039A1 (en) 2014-11-25 2016-06-02 Univation Technologies, Llc Methods of controlling polyolefin melt index
KR101731177B1 (en) * 2014-12-24 2017-04-27 주식회사 엘지화학 Transition metal compound having hetero atom, catalystic composition comprising the same, and methode for preparing polymers using the same
EP3294781B1 (en) 2015-05-08 2021-08-04 ExxonMobil Chemical Patents Inc. Polymerization process
WO2018063767A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063765A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018063764A1 (en) 2016-09-27 2018-04-05 Exxonmobil Chemical Patents Inc. Polymerization process
WO2018118155A1 (en) 2016-12-20 2018-06-28 Exxonmobil Chemical Patents Inc. Polymerization process
US11591417B2 (en) 2017-12-13 2023-02-28 Exxonmobil Chemical Patents Inc. Deactivation methods for active components from gas phase polyolefin polymerization processes
WO2019173030A1 (en) 2018-03-08 2019-09-12 Exxonmobil Chemical Patents Inc. Methods of preparing and monitoring a seed bed for polymerization reactor startup
CN112055720B (en) 2018-05-02 2022-11-22 埃克森美孚化学专利公司 Method for scaling up from pilot plant to larger production facility
US11447587B2 (en) 2018-05-02 2022-09-20 Exxonmobil Chemical Patents Inc. Methods for scale-up from a pilot plant to a larger production facility
WO2020014138A1 (en) 2018-07-09 2020-01-16 Exxonmobil Chemical Patents Inc. Polyethylene cast films and methods for making the same
CN112469556B (en) 2018-07-26 2023-05-02 埃克森美孚化学专利公司 Multilayer foam film and method for producing same
EP3880738A1 (en) 2018-11-13 2021-09-22 ExxonMobil Chemical Patents Inc. Polyethylene blends and films
CN113195603B (en) 2018-11-13 2023-05-26 埃克森美孚化学专利公司 Polyethylene film
WO2020163079A1 (en) 2019-02-06 2020-08-13 Exxonmobil Chemical Patents Inc. Films and backsheets for hygiene articles
WO2021126458A1 (en) 2019-12-17 2021-06-24 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved sealing performance and mechanical properties
US20230097375A1 (en) 2020-03-12 2023-03-30 Exxonmobil Chemical Patents Inc. Films made of polyethylene blends for improved bending stiffness and high md tear resistance
CN111747981A (en) * 2020-07-21 2020-10-09 万华化学集团股份有限公司 Transition metal compound and preparation method and application thereof
CN117098785A (en) 2021-04-30 2023-11-21 埃克森美孚化学专利公司 Method for transitioning between different polymerization catalysts in a polymerization reactor

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5376612A (en) * 1989-08-10 1994-12-27 Phillips Petroleum Company Chromium catalysts and process for making chromium catalysts
US5438027A (en) * 1991-12-13 1995-08-01 Phillips Petroleum Company Chromium compounds and uses thereof
US5434116A (en) * 1992-06-05 1995-07-18 Tosoh Corporation Organic transition metal compound having π-bonding heterocyclic ligand and method of polymerizing olefin by using the same
EP0590486A3 (en) * 1992-09-24 1994-08-24 Idemitsu Kosan Co Polymerization catalysts and process for producing polymers
EP0617052B1 (en) * 1993-03-23 1998-06-03 Asahi Kasei Kogyo Kabushiki Kaisha Olefin polymerization catalyst having a multidentate ligand

Also Published As

Publication number Publication date
RU2164228C2 (en) 2001-03-20
EP0799250B1 (en) 2001-03-21
WO1996020223A3 (en) 1996-09-06
JPH11507084A (en) 1999-06-22
CN1173186A (en) 1998-02-11
FI973660A (en) 1997-09-11
WO1996020223A2 (en) 1996-07-04
FI973660A0 (en) 1997-09-11
BR9510288A (en) 1998-12-15
TW413685B (en) 2000-12-01
DE69520450T2 (en) 2001-09-06
ES2157355T3 (en) 2001-08-16
AU4609896A (en) 1996-07-19
EP0799250A2 (en) 1997-10-08
US5539124A (en) 1996-07-23
DE69520450D1 (en) 2001-04-26

Similar Documents

Publication Publication Date Title
CA2208100A1 (en) Azametallocene polymerization catalysts
US6316556B1 (en) Homogeneous olefin polymerization catalyst composition
EP0822946B1 (en) Azaborolinyl metal complexes as olefin polymerization catalysts
JP4689829B2 (en) Crosslinked metallocenes for olefin copolymerization
US6992035B2 (en) Metallocenes, polymerization catalyst systems, their preparation, and use
KR100677869B1 (en) Multinuclear metal compound, catalyst system including the same, and olefin polymerization process using the same
JPH11501339A (en) Borabenzene olefin polymerization catalyst
JP4234327B2 (en) Polymerization process using improved bulky ligand metallocene-type catalyst system
EP0874003A1 (en) Process for co-polymerization of olefins
KR20020063279A (en) Mixed ziegler/metallocene catalysts for the production of bimodal polyolefins
JP2008519092A (en) Organochrome / metallocene combined catalyst for production of bimodal resin
JP2005502777A (en) Phosphinimine-supported polymerization catalyst
JP2018521192A (en) Process for preparing polyolefins having one or more pendant functional groups
US6214953B1 (en) Process for the preparation of olefinic polymers using supported metallocene catalyst
US6583242B2 (en) Supported olefin polymerization catalysts
US6500906B1 (en) Olefin polymerization chelate catalyst and olefin polymerization method using the same
US20050003950A1 (en) Method of making mixed ziegler-natta/metallocece catalysts
US6506858B1 (en) Olefin polymerization catalyst material and process for its preparation
EP0863920B1 (en) Process for the preparation of olefinic polymers using metallocene catalyst
JP2002510700A (en) Cyclopentadienyl transition metal compounds as polymerization catalysts
JPH08231619A (en) Polymerization of olefin
US5914408A (en) Olefin polymerization catalysts containing benzothiazole
US6008394A (en) Sulfonyl catalysts and method of using the same
KR20120075937A (en) Metallocene compound, catalyst composition including the same, and olefin polymerization process using the same
US7078469B2 (en) Halogenated organic particles for catalyst supports

Legal Events

Date Code Title Description
EEER Examination request
FZDE Discontinued